CH652048A5 - NON-AQUEOUS FLUID SYSTEM. - Google Patents

Description

40 The present invention relates to a non-aqueous fluid system which contains a non-aqueous composition and an organophilic clay as a rheologically active additive. This additive is the reaction product of an organic cationic compound with a smectite-type clay.

In preferred embodiments, the non-aqueous fluid system of the invention may be a paint composition, an organic printing ink, a lubricating oil, or a seal formulation based on polyvinyl chloride homopolymers and / or copolymers, the 50 non-aqueous composition being the film-forming material.

The paint composition and the organic printing ink usually additionally contain a finely divided pigment or an ink coloring material, these being dispersed in the film-forming material.

55 In general, non-aqueous fluid systems are greases, oil-based sludges, oil-based sealing liquids, paint removers, paints, stains, glazes, waxes, epoxies, sand binders for foundry mold manufacture, adhesives, sealants, inks, polyester laminate 60 resins, polyester gel coatings etc.

These fluid systems often also contain finely divided suspended materials, such as. B. pigments and the like. A rheologically active agent should be added to these systems in order to thicken the system and to ensure a thixotropic flow behavior with high viscosity at low shear forces. Various organically modified clays and other inorganic and organic compounds have been used to effect such theological effects.

Hitherto known agents for influencing the theological properties as well as suspending agents have various disadvantages which are overcome with the non-aqueous fluid systems according to the invention. So z. B. Aluminum stearate in terms of its ability to keep pigments in suspension in most organic carrier materials, and in terms of the ease with which pigments can be redispersed after they have settled from such suspensions due to longer aging times, is not entirely satisfactory. The gel, which is produced by introducing aluminum stearate into organic carrier materials, has rather a rubber-like character and not the properties of the desired thixotropic gel type, which is effective for maintaining stable suspensions. The presence of aluminum stearate in pigment suspensions, e.g. B. paints, has no advantageous effect compared to the brushing property of such suspensions. Organic derivatives of montmorillonite have also been used as suspending agents. However, such derivatives are generally only effective in the presence of aromatic and polar solvents and, accordingly, are ineffective when incorporated into the currently preferred odorless aliphatic hydrocarbon carrier materials.

In particular, the organophilic clays known from the prior art required the use of polar solvent activators, which had to be added to the system in order to ensure the theological effect. If the polar solvent activators were not used, the desired theological properties, namely the increase in viscosity, the prevention of pigment deposition and the prevention of dripping or running off, were not fully achieved, and this means that only a part of the Thickening properties of the clay was exploited. In addition, when the polar solvent activator was omitted from prior art compositions containing organoclay compounds, there was an increase in viscosity upon storage, and accordingly an adverse effect on the original theological properties that were to be imparted to the system. Some of these polar additives, such as Acetone, alcohols and the like have low flash points and should be avoided if possible. In addition, these polar additives would have to be added in a separate process step when preparing the systems mentioned. This separate process step contributes to increasing the respective costs of the systems. In addition, certain polar additives can react with other components of the system formulation and, accordingly, essential rheological properties can be lost.

Hydrogenated castor oil is a much more effective suspending agent than the montmorillonite derivatives mentioned, and it is suitable for use together with aliphatic hydrocarbon carrier materials. However, hydrogenated castor oil has the disadvantage that it is unstable at elevated temperatures, as is the case when processing suspensions, e.g. B. in paint factories, and it causes sand roughness or the formation of small granules in such suspensions, and such a loss of smoothness is highly undesirable in most suspensions, including those used in protective coatings in the area of inks be applied. Polyethylene has also been tried as a suspending agent, but this too has drawbacks in this regard. For example, paints that contain polyethylene as a suspending agent are characterized in that the pigment contained settles within a few days, that the draining or Prevention of runoff is only slight and they show little or no impact we3 652 048

during the initial processing of the paint components or after, the term "whipping effect" being understood to mean the desired appearance of a paint which indicates good dispersion and has an appearance which is similar to whipped cream. From the above, it is clearly evident that no theological agent known in the art is fully satisfactory or effective for a variety of non-aqueous fluid systems.

The present invention relates only to a non-aqueous fluid system containing an organophilic clay as a rheologically active additive and it is no longer necessary to add a polar solvent activator. These rheologically active additives are described in US-15 Patent No. 4412018, 4434076 and 4434076.

The non-aqueous fluid system according to the invention is characterized in that it contains a non-aqueous composition and an organophilic clay as a rheologically active additive, the additive being a reaction product of an organic cationic compound with a smectite-type clay which has a cation exchange capacity of at least 75 milliequivalents per 100 g of said clay and said organic cationic compound contains the following groups 25:

a) a first group containing an optionally substituted β / y-unsaturated alkyl or cycloalkyl group with up to 6 carbon atoms or a hydroxy-substituted alkyl or cycloalkyl group with up to 6 carbon atoms with an aromatic

30 table radical may be substituted,

b) a second group which is an optionally substituted saturated or unsaturated alkyl group having 12 to 60 carbon atoms,

c) a third and fourth group, which comprises the following groups:

the groups mentioned under a), optionally substituted aralkyl groups, optionally substituted alkyl or cycloalkyl groups having up to 22 carbon atoms and mixtures thereof,

40 and wherein the amount of the organic cationic compound is 90 to 140 milliequivalents per 100 g of the clay, based on 100% active clay.

The clays used to make the organophilic clays are smectite-type clays with a cation exchange capacity of at least 75 milliequivalents per 100 g of clay. Particularly desirable types of clays are the naturally occurring Wyoming variety of swelling bento-nit and similar clays, as well as hectorite, a swelling magnesium-lithium silicate clay.

50 The cation exchange capacity of the clays of the smectite type can be determined using the well known ammonium acetate method.

The clays, and in particular the bentonite-type clays, are preferably converted into the sodium form if they are not already in this form. This can be done easily by making an aqueous clay slurry and passing this slurry through a bed of cation exchange resin in the sodium form. Alternatively, the clay can be mixed with water and a soluble sodium compound, e.g. As sodium carbonate, sodium hydroxide and the like, and then exposing the mixture to shear forces, for example with an extruder.

Clays of the smectite type are either of natural origin 65 or they are produced synthetically according to the pneumatholytic or preferably according to a hydrothermal synthesis process. Typical examples of such clays are montmorillonite, bentonite, peidellite, hectorite, saponite and stevensite.

652 048 4

Synthetic clays can be hydrothermally 3-hydroxycyclohexyl; 4-hydroxycyclohexyl; 2-Hydroxycyclo-ren be prepared by using an aqueous reaction pentyl; 3-hydroxy-cyclopentyl; 2-methyl-2-hydroxypropyl; schungin form a slurry containing 1,2,2-trimethyl-2-hydroxypropyl; 2-phenyl-2-hydroxyethyl;

mixed hydrates or hydroxides of the desired metals with 3-methyl-2-hydroxybutyl; and 5-hydroxy-2-pentenyl.

or without sodium or other interchangeable cations or 5 The long-chain alkyl radicals can contain branched or unmixed mixtures thereof, fluoride in proportions which are desired for the respective branched, saturated or unsaturated, substituted or unsubstituted smectite to be produced synthetically. They are, and contain 12 to 60 carbon atoms. The long-chain slurry can then be introduced into an autoclave. Alkyl residues can be obtained from natural oils and under autogenous pressure to a temperature in the range of finally different vegetable oils, such as. B. corn oil,

about 100 to 325 ° C, preferably to 274 to 300 ° C, while heating 10 coconut oil, soybean oil, cottonseed oil, castor oil and for a sufficient period of time to obtain the similar as well as from various animal oils or desired product. Fat, like B. tallow oil. The alkyl residues can also be petrochemical

The organic cationic compounds, which are of organic origin, such as. B. from alpha olefin.

nophilic clay can be selected from a wide range. Typical examples of useful branched saturated residues of materials capable of being 15 are 12-methylstearyl and 12-ethylstearyl. Typical examples to give organiphilic clay and by exchanging cations for useful branched unsaturated residues are 12-methyloleyl with the smectite-type clay. The organic cationic and 12-ethyloleyI. Typical examples of unbranched sown compounds must have a positive charge, which are residues: lauryl; Stearyl; Tridecyl; Myristyl (tetradecyl); pentadecyl on a single atom or a small group of atoms; Hexacdecyl; Residues of hydrogenated tallow oil and localized from within the compound. This is preferably docosan oil. Typical examples of unbranched unsaturated organic cation selected from the group consisting of and substituted radicals are oleyl, linoleyl; Linolenyl, residues of quaternary ammonium salts, phosphonium salts and of soybean oil and tallow oil.

Mixtures of these consist, as well as of equivalent salts. The remaining groups of positively charged atoms and the organic cation, in particular at least one, are preferably selected from (a) a representative of the constituent, selected from (a) β-y-unsaturated alkyl groups 25 group from β, y-unsaturated alkyl groups and or hydroxyalkyl groups with up to 6 carbon atoms and hydroxyalkyl groups with 2 to 6 carbon atoms, both as (b) has a long-chain alkyl group. The remaining ones described above; (b) an alkyl group with up to 22 carbon moieties on the central positive atom are preferably exfoliated, cyclic and acyclic and (c) an aralkyl group, selected from a member of group (a), as described above, namely benzyl and substituted Enter benzyl groups, or an aralkyl group and / or alkyl group with 1 to 22 30 finally compounds with condensed nuclei, which carbon atoms. straight-chain or branched chains with 1 to and with 22

The preferred β-y-unsaturated alkyl groups can have a wide range of materials selected from carbon atoms in the alkyl portion of the structure. These typical examples of aralkyl groups are benzyl and substi-compounds can be cyclic or acyclic, unsubstituted benzyl groups and they include benzyl and or with aliphatic radicals that contain up to three carbon atoms 35-like materials containing, for example, benzyl halides, so that they can be substituted the total number of aliphatic benzhydryl halides, trityl halides, 1-halogeno-l-phenic carbon atoms in β-y-unsaturated radicals, preferably nylalkane, in which the alkyl chain 1 to 22 carbon atoms is 6 or less. The ß-y-unsaturated alkyl radical may have, such as. B. 1-halo-1-phenylethane; 1-halo-l-phe-be substituted with an aromatic ring, which may be nylpropane and 1-halo-l-phenyloctadecane as substituted if conjugated with the unsaturated ß-y group, or 40 benzyl groups, which are different from orto, Meta- and parachlor-the ß-y residue can be combined with an aliphatic residue and benzyl halides, orto, meta- and paranitrobenzyl halide

be substituted with an aromatic ring. den and Orto, meta and para alkylbenzyl halides, in

Typical examples of cyclic β-y-unsaturated alkyl groups which contain the alkyl chain from 1 to and with 22 carbon atoms include 2-cyclohexenyl and 2-cyclopentenyl. contains derivate and multinuclear cyclic benzyl-like Grup-Typical examples of acyclic ß-y-unsaturated alkyl groups, 45 pations, as they contain 2-halomethylnaphthalene, 9-containing 6 or fewer carbon atoms, are propargyl; Halomethylanthracene and 9-halomethylphenanthrene alkyl (2-propenyl); Crotyl (2-butenyl); 2-pentenyl; 2-hexenyl; derive, wherein the halogen atom is chlorine, bromine, iodine or 3-methyl-2-butenyl; 3-methyl-2-pentenyl; 2,3-dimethyl-2-bute- can be any other such moiety which is nyl; butenyl; l, l-dimethyl-2-propenyl; 1,2-dimethyl-2-prope leaving group in the nucleophilic attack of the benzyl group nyl; 2,4-pentadienyl; and 2,4-hexadienyl. Typical examples of 50 serve in such a way that the nucleophilic reagent are the leaving acyclic aromatically substituted compounds: Cinna group replaces in the benzyl-like grouping.

moyl (3-phenyl-2-propenyl); 2-phenyl-2-propenyl and 3- (4- Typical examples of useful alkyl groups which are linear

Methoxyphenyl) -2-propenyl. Typical examples of aromatic branched chain or cyclic and acyclic above, and aliphatic substituted materials are: 3-phenyl-2- are for example methyl; Ethyl; Propyl; 2-propyl; Isobutyl;

cyclohexenyl; 3-phenyl-2-cyclopentenyl; l, l-dimethyl-3-phe-55 cyclopentyl and cyclohexyl.

nyl-2-propenyl; l, l, 2-trimethyl-3-phenyl-2-propenyl; 2,3- The alkyl radicals can also be derived from other neutral oils,

Dimethyl-3-phenyl-2-propenyl; 3,3-dimethyl-2-phenyl-2-prope- both substituted and unsubstituted, derived wer-nyl; and 3-phenyl-2-butenyl. the, e.g. the ones described above, including various

The hydroxy-alkyl group is preferably selected from those animal and vegetable oils, e.g. Tallow oil, corn oil, with hydroxyl-substituted alkyl and cycloalkyl groups, with 60 soybean oil, cottonseed oil, castor oil and the like, such as the hydroxyl group with a carbon atom - also from various animal fats.

Which is in connection with the positively charged atom. There are many processes for the production of organi and which up to 6 aliphatic carbon atoms on known cationic salts are known. For example, the sen. The alkyl group can be quaternary ammonium salts with a aromatic ring substi expert by being one second. Typical examples include: 2-hydroxy-65-dialkylamine, for example by the hydrogenation of ethyl (ethanol); 3-hydroxypropyl; 4-hydroxypentyl; 6-hydro-nitriles, see US Pat. No. 2,355,356 xyhexyl ; 2-hydroxypropyl (isopropanol); 2-hydroxybutyl; and then the methyl dialkyl tertiary amine by reductive alkyl

2-hydroxypentyl; 2-hydroxyhexyl; 2-hydroxycyclohexyl; lation using formaldehyde as the source of

5,652,048

Methylrestes produces. See also Shapiro et al US Pat. No. Millie equivalent ratio defines the number of millie-3136 819 for the production of the quaternary amine halide equivalent (ME) of the organic cation in the organophilic by adding benzyl chloride or benzyl bromide to one clay per 100 g clay, calculated on the basis of 100% active tertiary amine and see also Shapiro et al. U.S. Pat. No. Sound, is. The organophilic clays described have one

2775 617.5 milliequivalent ratio of 90-140, and preferably of

The anion of the salt is preferably selected from the group 100-130. At low milliequivalent ratios, those are selected which do not consist of chloride, bromide and mixtures thereof organophilic clays so produced, and especially preferred, although chloride is also effective, although it is a good gelling agent, other anions, e.g. Acetate, hydroxide, nitrite and the like, when present in the usual way together with polar in the organic cationic compound, can be dispersed in dispersants. At higher milliequi-can to neutralize the cation. A typical formula for valent ratios are the organophilic clays poor gelation - the following is: remedy. However, it should be noted that the milliequivalent

ratios in the range of 90-140 can change depending on the characteristics of the organic system to be gelled with the organo-15 phile clay.

The way in which the organic cations perform their function in the organophilic clay mentioned is not completely known. From the unique properties which occur in the systems according to the invention, however, it is assumed that the electron-withdrawing and donor portions of the cation and in particular the unconditional presence of at least one long-chain alkyl group which is associated with a β-y-unsaturated alkyl group and / or the Hydroxyalkyl group is coupled are responsible. When bound to a positive atom selected from the group in this formula, the long chain alkyl group which β-y-unsaturated alkyl groups and hydroxyalkyl group can function as an electron donor which helps pen with up to 6 carbon atoms includes; R2 is a long chain to delocalize the positive charge. It is even more important that the alkyl group has 12 to 60 carbon atoms; R3 and R4 this enables the clay scales to be separated sufficiently from a group which can become the meanings, which includes a further subdivision under mild R] and, furthermore, aralkyl groups and alkyl shear conditions are possible. In contrast, the groups with 1 to 22 carbon atoms; X is a phosphorus-ß-y-unsaturated alkyl group to delocalize the positive or nitrogen atom and M "means CI", Br ", NO2", OH "or charge, which can lead to resonance and / C2H3O2". or inductive effect on the unsaturated alkyl group

The organophilic clays mentioned can be produced occurs. This effect does not occur to any significant extent by using the clay, the quaternary ammonium compound 35 or any previously known saturated alkyl groups. and water mixes with one another, preferably at a temperature. The improved action of the short-chain hydroxyalkyl group ratures in the range between 20 and 100 ° C. and in particular appears with the internally covalently bound polar activation

preferably in the range between 35 to 77 ° C, namely during the group, namely the hydroxyl group, if they are not related to a period of time sufficient for the organic positively charged atom to be adjacent.

Compounds coated the clay particles and then 40 This effect is suppressed when the hydroxyl group is filtered, washed, dried and ground. At the carbon atom, which is attached to the positively charged

Use of the organophilic clays in emulsions can connect the atoms or can be omitted from an aliphatic alkyl carbon, drying and grinding steps. which is more than 6 carbon atoms long.

If you e.g. B. the clay, the quaternary ammonium compound The organophilic clays explained above have a widespread use and water in such concentrations 43 as rheologically active additives that does not form a slurry, then non-aqueous fluid systems can also be used. The non-aqueous fluids of filtration and the washing step are omitted. Compositions in which the self-activating organic

The clay is preferably useful in water in a concentration of nophilic clays, are dispersed from about 1-80% and preferably from 2-7%, and for example paints, varnishes, glazes, waxes, the slurry is optionally centrifuged so as not to 50 epoxy resins, mastics, adhesives, cosmetics, inks, polyester, clay-like impurities to remove, which about 10 to laminate resins, polyester gel coatings and the like. These approximately 50% of the clay fluid starting material can be made in any conventional manner, and the slurry is then stirred and heated. B. in the US

to a temperature in the range from 35 to 77 ° C. Patent specification No. 4208 218, including the quaternary amine salt, can then be added in the desired milliequivalents of colloid mills, ball mills, roller mill ratio, and preferably in liquid form - And high-speed dispersers in which the pig-ger form is dispersed in isopropanol or in water, and it is further stirred well dispersed ment materials in the organic carrier material to effect the reaction. due to the high shear forces involved in processing

For ease of handling, it is preferred that the device be applied. While the present invention total organic material content in the reaction product 60 relates to non-aqueous fluid systems (liquids, flowable namely in the organophilic clay, less than about 50% by weight of the compositions and the like), however, it is solid-organophilic clay. Although higher proportions can be used, such compositions are also smaller, the reaction products are difficult to filter, dry in proportions of water, contained in a non-aqueous fluid medium and ground. can, such as B. amounts up to 10 wt .-% and such

The amount of organic cations making up the clay 65 compositions are the subject of the present invention.

usually added for processing, must be mature.

to give the clay the improved dispersion characteristics. The organophilic toning agent will be in those systems that are desired. This amount is used as men in amounts sufficient to make up the

652 048

to obtain desired theological properties, e.g. high viscosity with low shear force, prevention of dripping or running off of the fluid film and prevention of settling and hard packing of the pigment, which is present in the non-aqueous fluid composition. The amounts of organophilic toning agent used in the non-aqueous fluid systems should preferably range between about 0.1 and 15% by weight of the treated non-aqueous fluid system, and preferably the percentages are between 0.3 and 5.0% to give the desired theological effects.

The organophilic clays used as thickeners are characterized by a number of advantages over previously known and available suspending agents. Such advantages become apparent due to the improved processing properties shown by a variety of specific products, all of which are covered by the inventive concept. In general, the suspending agents mentioned do not form any granules or sand and are also not subject to any undesirable changes at high processing or storage temperatures; they act as effective gelling agents in the absence of solvent activators; they are effective both in aliphatic and in aromatic carrier materials, as well as in moderately polar carrier materials; their use allows full control and adjustment of theological properties and consistent results are obtained. In addition, and depending on the product properties and the ultimate desired use, they are non-yellowing and can be used without a decolorization step and they impart improved suspension properties to the materials thus produced, which gives excellent pigment suspension and excellent properties for preventing dripping .

Coating compositions which contain a film-forming organic and / or inorganic binder, solvent and optionally pigments have hitherto been described for use as decorative and / or protective materials, for example for metal, wood, plastics and paper. In practice, these compositions are applied to the substrate using devices such as e.g. Brushes, paint brushes, rollers or by airless or airless atomization or immersion. In these compositions, thixotropic gelling agents can be used which ensure a low viscosity of the coating composition at high shear forces, e.g. B. are used during the application of the coating, but they provide a high viscosity under low or without shear stress.

So far, asbestos, sublimed silica gel, various organic materials and organophilic clays have been used as effective gelling agents for such compositions. However, these materials suffered from various drawbacks, e.g. B. health risks, high costly embodiments and the preparation of unsuitable coating compositions which lack gloss and surface smoothness.

The organophilic clays contained in the system according to the invention could be used as effective gelling agents for coating compositions without the difficulties which are common with the materials known from the prior art. The organophilic clays can be dispersed in the coating composition using low, or, if desired, high shear forces.

In a typical procedure, the organophilic toning agents are added to a portion of the coating composition containing a film-forming organic binder, organic solvent, and optionally pigments, using mixing at a rate of approximately 1640 linear meters per minute 5. The stirring speed is increased to approximately 4920 linear meters per minute in order to ensure complete dispersion of the organophilic clays. After the dispersion is reached, the remaining amount of organic binder and solvent is added under low or medium shear conditions to complete the formulation. While this typical mode of operation is compatible with the use of the systems according to the invention, these systems according to the invention can alternatively also be added subsequently to a previously produced coating composition under low to medium shear conditions. This subsequent addition method is quite unexpected and not possible with the organophilic clay materials that have been customary to date, because they do not reach the full viscosity ranges and dispersion in the absence of high shear forces.

20th

The film-forming organic binders can be prepared by customary procedures, such as. B. by polymerization of acrylate and methacrylate esters from unsaturated polyester resins and / or by reaction of drying-25 the oils, such as. B. linoleic acid with polymers containing hydroxyl groups. In general, organic binders which have a molecular weight of 200 to several hundred thousand can be used.

Preferred organic solvents for such coatings can be broadly divided into five categories, which are aliphatic, aromatic, weakly polar, polar and chlorinated solvents. Aliphatic solvents usually include normal chain and branched chain aliphatic hydrocarbons having 5-12 carbon atoms and cycloali-35 phatic compounds. Aromatic solvents are usually such materials as. As benzene, toluene, xylene and ethylbenzene. Weakly polar solvents are e.g. B. ketones and ester solvents such as. B. acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, acetic acid, ethyl ester, butyl acetate, ethoxyethyl acetate and the like. Polar solvents are typically such materials as low molecular weight alcohols such as e.g. Methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol and ethoxyethanol. Chlorinated hydrocarbon solvents are usually 45 materials, such as. B. methylene chloride, chloroform, carbon tetrachloride, chloroethane and 1,1,1-trichloroethane.

These coating compositions can contain conventional additives, such as. B. finely divided solid particles that are to be suspended by the active ingredients. The finely divided additives which can be used, e.g. As pigments, extenders, inert substances, fillers, substances that increase the hiding power, etc., are all well known in the art and do not form part of the present invention.

The amounts of organophilic toning agent used in the coating compositions preferably range from 0.25 to 10%, and especially from 0.5 to 5%. Amounts greater than 10% can be used but are difficult to handle due to the high 60 viscosities. Organic binders can conveniently be used in amounts of 10-80% of the liquid portion of the coating composition. The organic solvent is usually used in an amount sufficient to reduce the viscosity of the coating composition to acceptable levels, depending on the method of application, but in any case it is used to make up the total composition to 100% . Additional additives, including pigments, can be used in amounts of

652 048

0.5-50% of the total coating composition can be used.

The theological additive to be used and the amount thereof in order to ensure satisfactory behavior of the respective coating composition varies due to various factors. In general, it has been found that an acceptable behavior with high polar solvent systems is achieved if the organophilic clay reaction products from quaternary compounds described which contain two or three long-chain alkyl groups are used. In contrast, quaternary compounds containing only a long-chain alkyl group have proven to be favorable in moderately to low-polar solvent systems. Accordingly, the nature of the suitable organic theological additive depends on the coating rheology desired, the type of solvent, the processing temperature and the manufacturing equipment. While the effectiveness of a particular theological additive varies depending on these factors, it has been found that the systems according to the invention have superior properties compared to previously known additives. In contrast to previously known materials, the systems according to the invention do not require any heat treatment during processing, they are less sensitive to heat during use and storage and they do not necessarily require the presence of polar activators and have an excellent viscosity build-up, anti-elimination effect and resistance Drops and drains are available.

Examples

The invention will now be explained in more detail with the aid of the following examples. All percentages given are by weight unless otherwise stated. The ingredients and amounts thereof used to prepare the respective coating composition are in Table IA (aliphatic pigmented solvent system), Table IIA (aliphatic clear solvent system), Table IIIA (aromatic pigmented solvent system), Table IVA (aromatic clear solvent system) and Table VA (weak polar clear solvent system).

The results in these tables show that the systems according to the invention, when they are subsequently added to a previously prepared coating composition, using relatively low shear forces, impart excellent viscosity and prevention of dripping or runoff to this composition and that dispersion of approximately the same degree is achieved than with the materials commonly used so far, if these are introduced into the system under significantly higher shear conditions. Likewise, the comparative materials, when introduced into the systems at lower shear conditions, are clearly inferior to the systems according to the invention with regard to dispersibility, viscosity build-up and resistance to dripping or runoff, if these are introduced using the same shear force.

The organophilic clays which are contained in the system according to the invention, as indicated in the tables,

were added subsequently and low shear forces were applied to the coating composition without the addition of a polar solvent activator. For comparison purposes, various previously customary organophilic clays were also subsequently added to the coating compositions, using the same shear conditions as the organophilic clays used here, but in this case a mixture of 95% methanol and 5%

10th

Water added as a polar solvent activator for the organotones.

Specifically, 600 g of a previously prepared coating composition containing no theological additive was prepared, and this amount was weighed into a round jug with a volume of approximately 0.951, which was approximately 10.16 cm in diameter and approx. 12.5 cm. The system was stirred using a 735,498 75 W Premier Dispersator equipped with a Cowles saw blade with a diameter of approximately 4.5 cm. The leaf was placed in the system in the center of the quart can at a height so that the bottom of the leaf was 1.27 cm above the bottom surface of the can. The speed of rotation was kept constant at 3000 revolutions per minute. 5.1 g of the organophilic clay described were slowly introduced into the stirring system. In the case of the comparative material, 1.7 g (2.1 cm3) of a mixture of 95% methanol and 5% water was also added to the system exactly one minute after the addition of the organophilic clay. This polar solvent activator was injected into the system using a 5 cm3 glass syringe.

The system plus organophilic clay plus activator, in the case of the 25 comparative experiment with the organophilic clay, was mixed at an axis speed of 3000 revolutions per minute for a total of 15 minutes. At this point, without stopping the disperser, a small aliquot of the solution was removed from the jug using a conical 30 spatula approximately 12.7 cm long made of stainless steel. This aliquot was used to measure the fineness of the dispersion of the solution. This measurement was carried out by using a Hegman fineness measuring device which had a scale of 0-8, where 0 corresponds to a film thickness of 35 0.203 mm and 8 corresponds to a film thickness of 0 mm. The grinding fineness measuring device is a stainless steel block in which a channel with different depths had been milled. The solution to be tested is placed in the channel at the lowest end and is poured 40 the full length of the channel. The fineness of the grinding of the system is determined at the point along the channel depth at which the pigment particles are first visible above the surface of the solution film. This measurement was carried out after a mixing time of 15 minutes. 45 The systems were then transferred to sheet metal containers and allowed to equilibrate overnight at 20 ° C before testing for viscosity and resistance to dripping or draining.

The ease of dispersion test was carried out as discussed above using a Brookfield RVT viscometer equipped with a # 4 spindle and the spindle speed was 10 revolutions per minute. The draining and draining measurements were carried out with a Leneta anti-drip blade. The drains 55 were poured onto “Leneta-7 B cards” using a mechanically driven film applicator equipped with a perforated vacuum plate. The full casts were placed in a vertical position with horizontal streaks of paint with the thinnest line on top. The 60 drip test evaluated after the film had dried and found the thickest strip that did not run out enough to penetrate the next strip below. The units for the drip test are given in mm.

Tables IB and IIB show the data of the coating systems produced, improved authenticity of the dispersion and / or greater viscosity buildup under moderate shear conditions compared to additives customary hitherto.

65

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In Tables Illb and IVB, the data show a general increase in the viscosity build-up and consistently improved anti-drip properties of the organophilic clays described in comparison to additives conventionally produced hitherto.

In Table VB, the data show essentially the same results compared to previously known additives with a limited number, which show increased viscosity build-up for the organophilic clays described.

Table IA

Aliphatic pigmented solvent system

Components

Common name

Manufacturer

Blank value (no thickener) kg

Comparative experiment Normal processing (high shear forces) kg

Experimental processing with low shear force kg

Starting materials Aroplaz 1266M70

Mineral spirits 663

Rheological additive

Langöl-So j a-alkyd resin solution (70% N.V.) Aliphatic hydrocarbon

Dimethyl di-hydrogenated valley gammonium bentonite

Spencer Kellogg Div. approx. 30.0 approx. 30.0

of Textron, Inc.

Union Oil Company of about 30.3 about 30.3

California

NL industries Inc. - -

Methanol / water 95/5 TITANOX 2020 Atomite approx. 109.0 approx. 86.8

Titanium dioxide rutile calcium carbonate natural,

ground

Grind at high speed - 5400 revolutions per minute for 15 minutes of draining - and add in the following order while stirring at 2000 revolutions per minute

NL Industries, Inc.Tompson, Weinmann & Co.

approx. 1.5 approx. 109.0 approx. 86.8

Mixing at 3000 revolutions per minute

Stir in thickener

Organophilic clay

Experimental total quantities approx. 478.9

about 485

about 30.0 about 30.3

approx. 109.0 approx. 86.8

Aroplaz 1266M70

Long Oil Soy Alkyd Resin

Spencer Kellogg Div.

approx.

109.8

approx.

109.8

approx.

109, i solution (70% N.V.)

of Textron, Inc.

Arofiat 3113PO

Thixotropic alkyd

Spencer Kellogg approx.

86.8

approx.

86.8

approx.

86.8

Mineral spirits 663

Aliphatic hydrocarbon

Union Oil Company of California approx.

21.2

approx.

21.2

approx.

21.2

Paint Drier

6% cobalt naphthenate

Tenneco Chemical, Inc.

approx.

0.8

approx.

0.8

approx.

0.8

Paint Drier

4% calcium naphthenate

Tenneco Chemical, Inc.

approx.

3.9

approx.

3.9

approx.

3.9

Exkin No. 2nd

Oxime skin preventing agent

Tenneco Chemical, Inc.

approx.

0.45

approx.

0.45

approx.

0.45

10.0

approx. 483.5

Table IIA Aliphatic Clear Solvent System

1. 388 g of Aroplaz 1266-M70 are poured into an unlined jug of approximately 0.951 contents.

2. It is stirred at 1000 rpm using a disperser with a 41.2 mm Hi-Vis blade with an output of 735.49875 W.

3. 12 g of rheological additive are added during mixing.

50

4. Increase the speed of the mixer blade to 3000 rpm.

5. After 1 min, 2 g of ethylene glycol are only added to the sample with sublimed silicon oxide.

6. Assessment of the fineness of the grinding after mixing for 15 minutes.

7. Transfer the flour into an unlined pot of approx. 0.471 content.

55 8. Brookfield viscosity measurement at 10 rpm for 5 min.

9. Determine the viscosity the next day.

Table IB

example

Rheological additive (ME ratio)

fineness

viscosity

Expire

the ver

10'3 Pas

(mm)

grinding

24 hours

24 hours

Comparative experiment A

Sublimated silicon dioxide

0

800

about 0.10

Comparative experiment B

Benzyl trihydrated tallow ammonium bentonite (111.5)

6

1250

about 0.15

Comparative experiment C

Benzyl trihydrogenated tallow ammonium bentonite (117.8)

6

1300

about 0.15

Comparative experiment D

Methyl trihydrogenated tallow ammonium bentonite (110.8)

2nd

1760

about 0.19

9 652 048

Table IB (continued)

example

Rheological additive (ME ratio)

fineness

viscosity

Expire

the ver

10 "1 Pas

(mm)

grinding

24 hours

24 hours

Comparative attempt E

Methyl trihydrated tallow ammonium bentonite 7116)

"~ 5 ~

1650

about 0.19

Comparative experiment F

Dimethyl dihydrogenated tallow ammonium bentonite (110)

0

480

about 0.08

example 1

Allyl trihydrogenated tallow ammonium bentonite (110.8)

5

1620

about 0.19

Example 2

Ethanol trihydrated tallow ammonium bentonite (111.8)

0

1360

about 0.15

Example 3

Allyl-benzyl-dihydrogenated tallow ammonium bentonite (110)

0

704

about 0.10

• Example 4

Allyl ethanol dihydrogenated tallow ammonium bentonite (108.8)

1

764

about 0.10

Example 5

Allyl-methyl-dihydrogenated tallow ammonium bentonite (119.8)

1.5

1496

about 0.19

Example 6

Ethanol-methyl-dihydrogenated tallow ammonium bentonite (108.2)

0

940

about 0.05

Table IIB

example

Rheological additive (ME ratio)

fineness

viscosity

Expire

the ver

IO "3 Pas

(mm)

grinding

24 hours

24 hours

Comparative experiment G

none

-

4540

about 0.10

Comparative experiment H

Sublimated silicon oxide

7.5

9900

about 0.10

Comparative Experiment I

Dimethyl dihydrogenated tallow ammonium bentonite (95)

0

5840

-

Comparative experiment J

Benzyl trihydrated tallow ammonium bentonite (111.5)

0

14120

about 0.31

Comparative experiment K

Methyl trihydrated tallow ammonium bentonite (111)

0

8800

about 0.15

Example 7

Allyl-benzyl-dihydrogenated tallow ammonium bentonite (110)

0

7040

about 0.13

Example 8

Allyl ethanol dihydrogenated tallow ammonium bentonite (108.8)

0

10260

about 0.18

Example 9

Allyl-methyl-dihydrogenated tallow ammonium bentonite (109.8)

0

16740

about 0.36

Example 10

Ethanol-methyl-dihydrogenated tallow ammonium bentonite (108.2)

0

7140

about 0.13

Table IIIA Aromatic pigmented solvent system

Components

Common name

Manufacturer

Blank value (no thickener)

kg

Usual procedure (high shear force)

kg

Processing with lower

Shear force

(subsequent

Encore)

kg

Starting materials are added in the following order

Duraplex 12-808

"Short oil" unmodified alkyd (60% N.V.)

Reichhold Chemical, Inc.

about 97.5

about 97.5

about 97.5

Xylene

-

Shell Chemical Co.

approx. 66.3

approx. 66.3

approx. 66.3

Rheological additive

Dimethyl dihydrogenated tallow ammonium hectorite

NL Industries

-

about 4.54

-

Methanol / water 95/5

-

-

-

1.5

Titanox 2020

Rutile titanium dioxide

NL Industries, Inc.

approx. 161

approx. 161

approx. 161

Machining in the ball mill for 16 h

Drain and add to the ball mill in the following order

Duraplex 12-808

"Short oil" unmodified alkyd (60% N.V.)

Reichhold Chemical, Inc.

about 89.9

about 89.9

about 89.9

Uformite 27-809

Melamine formaldehyde resin (50% N.V.)

Reichhold Chemical, Inc.

about 80.3

about 80.3

about 80.3

Mix in a ball mill for one hour before filling into cans

Thickener

Rheological additive

Experimental

_

-

about 4.54

stir

Mix into the finished paint using an attachment at 3000 rpm

Total quantities approx. 333.5

approx. 339.8

about 338.4

652 048

10th

Table HIB

example

Rheological additive (ME ratio)

fineness

viscosity

Ablau

the ver

10'3 fits (mm)

grinding

24 hours

24 hours

Comparison test

L

Sublimated silicon dioxide

3rd

2560

approx.

0.31

Comparison test

M

Benzyl trihydrated tallow ammonium bentonite (111.5)

0

760

approx.

0.20

Comparative attempt

N

Benzyl trihydrogenated tallow ammonium bentonite (117.8)

1.5

700

approx.

0.15

Comparative attempt

O

Methyl trihydrogenated tallow ammonium bentonite (110.8)

0

1340

approx.

0.18

Comparison test

P

Methyl Trihydrogenated Tallow Ammonium Bentonite (116)

4.0

2550

approx.

0.41

Comparison test

Q

Dimethyl dihydrogenated tallow ammonium bentonite (110)

0

420

approx.

0.10

Example 11

Allyl trihydrated tallow ammonium bentonite (111.8)

0

780

approx.

0.18

Example 12

Ethanol trihydrated tallow ammonium bentonite (111.8)

0

520

approx.

0.10

Example 13

Diallyl dihydrogenated tallow ammonium bentonite (108.4)

0

740

approx.

0.20

Example 14

Allyl-benzyl-dihydrogenated tallow ammonium bentonite (110)

0

700

approx.

0.15

Example 15

Allyl ethanol dihydrogenated tallow ammonium bentonite (108.8)

0

880

approx.

0.23

Example 16

Allyl-methyl-dihydrogenated tallow ammonium bentonite (109.8)

0

1300

approx.

0.25

Example 17

Ethanol-benzyl-dihydrogenated tallow ammonium bentonite (110)

2nd

1030

approx.

020

Example 18

Ethanol-methyl-dihydrogenated tallow ammonium bentonite (108.2)

1

830

approx.

0.20

Example 19

Triallyl hydrogenated tallow ammonium bentonite (110.6)

-

640

approx.

0.20

Example 20

Diallyl methyl hydrogenated tallow ammonium bentonite (108.1)

0

480

approx.

0.13

Example 21

Allyl-dibenzyl-hydrogenated tallow ammonium bentonite (111.8)

0

1550

approx.

0.23

Example 22

Allyl-diethanol-hydrogenated tallow ammonium bentonite (108.1)

0

440

approx.

0.13

Example 23

Allyl dimethyl hydrogenated tallow ammonium bentonite (110.3)

0

400

approx.

0.10

Example 24

Allyl ethanol hydrogenated tallow ammonium bentonite (109.8)

0

500

approx.

0.13

Example 25

Allyl-benzyl-methyl-hydrogenated tallow ammonium bentonite (108.5)

0

450

approx.

0.13

Example 26

Diethanol-benzyl-hydrogenated tallow ammonium bentonite (111.5)

0

440

approx.

0.13

Example 27

Ethanol-benzyl-methyl-hydrogenated tallow ammonium bentonite (109.2)

0

440

approx.

0.10

Example 28

Diethanol-methyl-hydrogenated tallow ammonium bentonite (111.7)

0

450

approx.

0.15

Example 29

Ethanol dimethyl hydrogenated tallow ammonium bentonite (108.1)

0

400

approx.

0.10

Table IVA Aromatic Clear Solvent System

1. Add 392 g of Duraplex 12-808 to an unclothed jug of approx. 0.951 contents.

2. Stir at 1000 rpm with 1 disperser with a 41.2 mm Hi-Vis blade with an output of 735.49875 W.

3. Add 12 g of theological additive while mixing.

4. Increase the speed of the mixer blade to 3000 rpm.

35

5. Check the fineness of the grinding after mixing for 15 minutes.

6. Transfer the gel into an unlined jug of approx. 0.471 content.

7. Measurement of the Brookfield viscosity at 10 rpm for 15 min.

8. Determine the viscosity the next day.

Table IVB

example

Rheological additive (ME ratio)

fineness

viscosity

Ablau

the ver

10'3 fits (mm)

grinding

24 hours

24 hours

Comparative experiment R

Sublimated silicon dioxide

0

12400

about 0.46

Comparative experiment S

Benzyl trihydrated tallow ammonium bentonite (111.5)

0

20320

about 0.51

Comparative experiment T

Benzyl trihydrogenated tallow ammonium bentonite (117.8)

0

11600

about 0.46

Comparative experiment U

Methyl trihydrated tallow ammonium bentonite (111)

7.5

20500

about 0.76

Comparative experiment V

Methyl Trihydrogenated Tallow Ammonium Bentonite (116)

7.5

21400

about 0.76

Comparative experiment W

Dimethyl dihydrogenated tallow ammonium bentonite (110)

0

9620

about 0.41

Comparative experiment X

Blank value

-

5760

about 0.31

Example 30

Diallyl dihydrogenated tallow ammonium bentonite (108.4)

1

21200

about 0.51

Example 31

Allyl-benzyl-dihydrogenated tallow ammonium bentonite (110)

0

12640

about 0.51

Example 32

Allyl ethanol dihydrogenated tallow ammonium bentonite (108.8)

0

18960

about 0.51

Example 33

Allyl-methyl-dihydrogenated tallow ammonium bentonite (109.9)

6

25320

about 0.64

Example 34

Ethanol-benzyl-dihydrogenated tallow ammonium bentonite (110)

1

21800

about 0.64

Example 35

Ethanol-methyl-dihydrogenated tallow ammonium bentonite (108.2)

0

14680

about 0.51

Example 36

Triallyl hydrogenated tallow ammonium bentonite (110.6)

0

21440

about 0.51

Example 37

Diallyl methyl hydrogenated tallow ammonium bentonite (108.1)

0

50000

about 0.51

Example 38

Allyl-diethanol-hydrogenated tallow ammonium bentonite (108.1)

0

21250

about 0.46

Example 39

Allyl dimethyl hydrogenated tallow ammonium bentonite (110.3)

0

39000

about 0.64

Example 40

Allyl ethanoi benzyl hydrogenated tallow ammonium bentonite (109.8)

0

40000

about 0.51

11

652 048

Table IVB (continued)

example

Rheological additive (ME ratio)

fineness

viscosity

Ablau

the ver

10 "3 fits (mm)

grinding

24 hours

24 hours

Example 41

Allyl-benzyl-methyl-hydrogenated tallow ammonium bentonite (108.5)

0

8000

about 0.41

Example 42

Diethanol-benzyl-hydrogenated tallow ammonium bentonite (111.5)

0

21000

about 0.41

Example 43

Ethanol-benzyl-methyl-hydrogenated tallow ammonium bentonite (109.2)

0

23000

about 0.46

Example 44

Diethanol-methyl-hydrogenated tallow ammonium bentonite (111.7)

0

7600

about 0.51

Example 45

Ethanol dimethyl hydrogenated tallow ammonium bentonite (108.1)

0

8400

about 0.51

Table VA Polar pigmented solvent system

Components

Common name

Manufacturer

Processing with low shear force (kg)

toluene

Methyl ethyl ketone 95% 2-propanol isobutyl acetate approx. 54 150.0 approx. 80 12.5 approx. 5.64 292.0 approx. 132.9

Stir at low speed using a Cowles stirrer in a one-gallon paint pot.

Binyl VAGN resin polyvinyl chloride resin Union Carbide approx. 63.5

Introduce into the solvent mixture with stirring using the Cowles stirrer. Seal the can and rollers overnight to complete the solution of the resin. Transfer to a ball mill.

ONCORM50 (Registered Goods- Basic Lead Silicochromate NL Industries, Inc. approx. 45.6

characters from NL)

Indian Red # 5098 Red iron oxide Pfizer 9.4 approx.4.3

Tricresyl phosphate - Stoney-Mueller 14.5 approx.6.7

Epichlorohydrin - - 1.0 approx.0.45

Placing in a ball mill and grinding with it for 16 h to a Hegman fineness of 5 or better.

Organophilic clay - Experimental approx.4.54

Mix in the raw paint using a Cowles stirrer at a speed of 3000 rpm for 15 min.

Table VB

example

Rheological additive (ME ratio)

fineness

viscosity

Ablau

the ver

(10 "3 Pas)

fen (mm)

grinding

24 hours

24 hours

Comparative experiment Y

Sublimated silicon dioxide

4th

5540

about 0.89

Comparative experiment Z

Dimethyl benzyl hydrogenated tallow ammonium bentonite (102)

0

4480

about 0.76

Comparative experiment A A

Methyl benzyl dihydrogenated tallow ammonium bentonite (112)

0

1600

about 0.51

Example 46

Diallyl dihydrogenated tallow ammonium bentonite (108.4)

0

1420

about 0.46

Example 47

Allyl-methyl-dihydrogenated tallow ammonium bentonite (109.9)

0

1600

about 0.51

Example 48

Ethanol-benzyl-dihydrogenated tallow ammonium bentonite (110)

0

1300

about 0.46

Example 49

Triallyl hydrogenated tallow ammonium bentonite (110.6)

0

6000

about 0.89

Another specific embodiment of the present invention relates to the manufacture of non-aqueous fluid systems for printing ink compositions.

The dispersion of finely divided pigments, i.e. of printing ink coloring material in organic ink carrier materials for the production of a material which is suitable as printing ink is an extremely complex technical process. The type of surface to be printed, the printing press used in each case, the speed of the operation and the drying time are all essential factors which determine the necessary work qualities for a satisfactory ink.

The proliferation of modern newspapers has led to the development and use of high speed printing presses in the printing industry. This calls for printing inks that dry quickly. Resin-based systems, which can be dried by water, steam or hot air, are gradually displacing the conventionally used drying oils. Modern high-speed presses require inks that dry in seconds rather than 65 minutes.

For high speed printing, the ink must have well-balanced stickiness, penetrability and strength. Too high stickiness can cause that

652 048 12

Paper tears, or the ink can cause fogging at high 75 milliequivalents per 100 g of said clay, whereby the

Print speeds. Inks with insufficient organic cationic compound named following group-

Stickiness is not re-printed cleanly in the printing process. stanchions contains:

If the depth of penetration of the ink is too large, the printing of a) becomes a first group, which shows a β, y-unsaturated cyclic or the back of the paper, or there may be a bleeding 5 acyclic substituted or unsubstituted alkyl group with up to figures . A poorly controlled depth of penetration to 6 carbon atoms or a hydroxy-substituted cyclic can lead to dirty printing after the ink has been dried artificially or acyclic alkyl group with up to 6 carbon atoms. An ink must represent a suitable body which can be substituted with an aromatic residue

to prevent them from being centrifugally driven at b) a second group that is thrown off an optionally substituted high printing speed. In contrast, 10 saturated or unsaturated alkyl groups with 12 to 60 carbon

too viscous inks do not flow in a suitable manner from the substance atoms,

Sources to the printing rollers. c) a third and fourth group, which the following groups

These variations of the conditions that must be met include:

sen, make it necessary that the ink industry a large, optionally substituted the group mentioned under a)

Number of formulations available. For example 15 aralkyl groups, optionally substituted alkyl or cyclo

US Pat. No. 2,750,296 bears a printing ink of open-alkyl groups with up to 22 carbon atoms and mixtures, which contains color-donating material which is present in one of them,

Carrier material, which is an oil-soluble resinous binder and the amount of the organic cationic compound

rial, dissolved in mineral oil, and wherein the carrier aging is 90 to 140 milliequivalents per 100 g of the clay, based on the still long-chain aliphatic amine bentonite, 20 of 100% active clay.

which contains 34 carbon atoms in the aliphatic chain. In these printing inks contain an organic ink carrier - in contrast, U.S. Patent No. 2754219 discloses the material dispersed therein with an ink dye and the described formulation of an anti-fog printing ink made by bene organophilic toning agents. The organic ink addition to an ink, the main carrier material of which contains a solvent and a binder, is a hydrocarbon component which is an aromatic solvent. B. contains high-boiling hydrocarbon content, a finely divided organic derivative of montages, as well as other common solvents, may be-morillonite, in which the organic substituent turns a chain of. The solvent is preferably one having at least 12 carbon atoms. In addition to these, the aliphatic solvent, or mixtures of such U.S. patents, U.S. Patent No. 2,733,967 discloses solvents because they are economical to use and hand-held, and contain a printing ink which has a modified tone to produce acceptable systems. Usual holds, which forms a gel in the organic carrier material and binders, such as. synthetic or natural resins, which essentially have the gel-like film-forming properties in this composition, can be used when applied. The previously known compounds have, however. These binders also serve as carriers for all of the various disadvantages. For example, some need pigment. The type of binder used depends on the undesirable use of polar dispersing agents, depending on the particular application, and can accordingly, which can react with other ink formulation components from drying oil varnishes, alkyd resins, polyester carriers and yeast so that essential ink properties lost urethane alkyds can be selected. Ink coloring materials go, while other diverse shear treatments include pigments or pre-dispersed pastes. The pre-dispersers of a roller mill require, in order to obtain a viscous paste, a pigment, a carrier material and an inert material, the viscosity of which contains 40 solvents when stored. Other additives can not increase in the, which causes high labor costs while at the same time - printing ink is introduced to the ink properties for low production settings. to modify special applications. These additives

In contrast to these previously known techniques, drying aids, dispersants, pigment extenders,

U.S. Patent No. 4,193,806 includes the manufacture of a gel and antioxidants.

The printing ink can contain rial and an organophilic toning agent which can be produced economically and practically by simply introducing the organophilic toning agent into the reaction product of a smectite-type clay, which is a base ink composition which is an ink coloring agent.

Cation exchange capacity of at least 75 milliequivalents rial and contains an organic ink carrier material, produced per 100 g of clay, and a methylbenzyldialkyl-ammo.

nium compound or a dibenzyl-dialkyl-ammonium compound. 50 The ink compositions which with the inventive

bond, whereby the alkyl groups 14-22 carbon atoms are produced according to systems, achieve high viscosity

contain. The printing inks, which are disclosed in this US patent level by merely disclosing the systems of the invention, are described as stirring the complete into the ink formulation and the passage through

Viscosity range obtained after passing through a three roll mill, or using other similar ones

Three-roll mill, in contrast to previous comparative gelling 55 systems to maintain an increase in viscosity are not among those in which the viscosity increases. While this is necessary.

Patented printing ink takes the state of the art to new levels. The product can be easily dispersed as a theological additive.

has raised, further improvements and advances are needed to achieve maximum viscosity formation by means of the need for a first treatment with high conventional dispersing devices in the absence of a

Shear forces to achieve an acceptable viscosity level 60 three-roll mill. By using the organo-

from executing, eliminating. In phile clays, ink compositions are available

A printing ink which provides a viscosity increasing additive which, when appropriately dispersed, contains particles has been unexpectedly found. These have a print size which is fine enough that no filtration or ink contains an organic ink carrier material which is ground therein in order to disperse a usable formulation, an ink coloring material and an organophilic clay 65 are obtained.

gelling agent, which is the reaction product of an organic During a three-roll mill in the dispersion of the ink

is cationic compound with a smectite-type clay, coloring pigments or materials can be applied

and it has a cation exchange capacity of at least such that the ink is satisfactorily printed on the

13

652 048

machine prints, and this procedure is usually necessary, so it is not necessary to pass through a three-roll mill to increase the viscosity.

Passing through a loosely set three-roll mill may be necessary, in some cases with ink systems that undergo oxidation so that no trapped air from the dispersion step can cause small cured particles to form in the ink.

The printing ink can also be obtained by adding the organophilic toning agent to a previously finished printing ink. These inks can be made by any of the usual methods, e.g. with colloid mills, roller mills, ball mills etc., where the ink pigment material is well dispersed in the organic ink carrier mass by the high shear forces applied in this procedure. This dispersion of the pigment in the carrier material results in a normal ink and has the usual tendency to fog.

The organophilic toning agent is usually used in amounts sufficient to achieve the desired viscosity and stickiness of the printing ink. If necessary, the viscosity can be further controlled by adding a viscosity reducing agent such as naphthenic oil or solvent. In general, amounts of 0.1-15% of the printing ink are sufficient to largely reduce the tendency to fogging of the ink when used in high-speed line printing presses, and a range of 0.5-4% is preferred, and a range is particularly preferred of 1-3%. If the gelling agent is used in concentrations of less than 0.1% or more than 10% of the printing ink, the consistency, flow behavior and other properties which influence the critical characteristics of the ink are significantly deteriorated and the desired increase in viscosity and stickiness is not achieved.

These printing inks can contain customary ink additives, as are used in such printing inks. For example, oil-soluble clays used to drown out the brownish hue of mineral oil and carbon black pigment, as well as small amounts of waxes or fats, can be used to impart special properties to the printing ink.

The printing inks mentioned which can be produced with the gelling agents described include, but are not limited to, those which are heat-setting or inks suitable for newspaper printing, water or steam-curing inks or lithographic printing inks.

Newsprint inks dry primarily through penetration and absorption, although some heat is used to accelerate drying and prevent imprints. By properly adjusting the viscosity, stickiness, and yield point of such inks, the described organophilic clays effectively provide a suitable depth of penetration without the occurrence of centrifugal ejection or fog.

When the organophilic clays are used with other heat imaging typographic inks such as e.g. high-quality inks for periodicals, which contain additives, such as B. binders plus solvents, these inks are extremely flexible, non-smudging, good drying and fast setting at high temperatures. Application of the gelling agent to steam or water-setting inks greatly affects viscosity and stickiness by causing the ink to become fragile.

In contrast, lithographic printing inks are very similar in composition compared to typographic

Inks, except that they have more opacity and the pigment concentration is higher. The advantages of using organophilic clays as mentioned above also apply in this case.

5 The following tests were used in the examples:

Dispersion

The test ink was filled through both channels of a grinding precision measuring device, namely “NPIRI G-1 grindometer”, and the fineness of the grinding (small particles) and scratches were assessed. The scale of the measuring device ranged from «10» to «0». A reading of 10 corresponds to a depth of 0.025 mm and a reading of 0 corresponds to a depth of 0. Samples were taken, in such a number that a minimum of 4 separate measured value readings were taken and these were averaged. Perfect measurement values for a test sample were “0” for both the fineness of the grinding and for scratches.

20th

30th

35

viscosity

The viscosity was determined using a Thwing-Albert Fallstab viscometer using a block temperature of 25.6 ° C. The air was removed from the ink by simply stirring with a spatula and then a stick was completely coated with the ink sample. Three weights were used to obtain fall time values: 700,500,200 g. The weight tests were repeated and the data processed on a Hewlett-Packard computer to give the predicted Bingham viscosity in Pascals at 1000 sec "1. The viscosity value selected for introduction to the tables became selected based on the data showing the smallest mean square deviations from a straight line calculated from the Bingham equation fB = T-DbMb, which indicates the intercept on the shear stress axis when the shear value is zero.

fB is the flow value 40 T is the shear stress Db is the shear value Mb is the viscosity

Printing Ink Preparation A red base web offset ink formulation that was 45 heat setting was prepared using the ingredients shown in Table VI, and this formulation was passed through a three-roll mill once to obtain a fine ink dispersion. The rheological additive was then slowly added to the base ink using the minimum possible agitation to prevent leakage. The dispersion was then obtained by stirring at 3000 rpm with a disperser (0.5 H.P. Premier Dispersator Unit) using a Cowles blade. A suitable rate was maintained for 15 minutes 55. Viscosity measurements were made after dispersion and after 24 hours.

Separate ink samples were treated with various organophilic clay derivatives and also reference materials at a dosage level of 2%.

60 In the comparative experiment BB, finely divided silicon oxide with the trade name Aerosil R972 (DeGussa Inc.) was used. In the comparative experiment CC, an organophilic clay was used, which is called benzyl-trihydrated tallow ammonium bento-nit. The compositions are given in Table 65 VII.

The data show that the material made from the quaternary compounds gave good dispersion and effectiveness when mixed under low shear conditions.

652 048

14

Table VI

Web offset, heat-setting base ink formulation - red

component

Manufacturer

Common name

% in the wording

Lo-Cal A-7-T

Lawter Chemicals

Heat-curing varnish

51

Heat Set Microwax Compound C-219 Dyall *

6

Heat set Fischer-Tropsch Wax C-188

Dyall *

Heat-setting Fischer-Tropsch wax

4th

Lithol Rubine 66-PP-0229

BASF Wyandotte

Heat-setting, pre-dispersed red paste

31

Ionol (15% w / v / in Magiesol e7)

Shell Chemical

Antioxidants

2nd

Magiesol 47

Magic Bros.

High-boiling, hydrocarbon solvent

4th

(average boiling point 470 ° F)

Rheological additive

Total base material

98.0% 2 0

Total of the finished mix

100.0%

* Dyall is a subsidiary of Lawter Chemicals

Table VI

example

Rheological additive (ME ratio)

Dispersion

viscosity

Delicacy of

Scrapes /

(0.1 Pas)

24 hours

Miss

time

Beginning

lung / time

Lich

Comparative ver

look for BB

Sublimated silicon dioxide

10/15

0/15

80

84

Comparative ver

such as CC

Benzyl trihydrogenated tallow ammonium bentonite (114)

0/5

0/5

86

88

Example 50

Allyl trihydrogenated tallow ammonium bentonite (116.1)

0/10

0/10

87

87

Example 51

Diallyl dihydrogenated tallow ammonium bentonite (108.4)

10/20

1 (4-0), 1 (2-0)

95

94

Example 52

Allyl-benzyl-dihydrogenated tallow ammonium bentonite (110)

10/20

0/20

99

98

Example 53

Allyl ethanol dihydrogenated tallow ammonium bentonite (108.8)

10/20

1 (3-0), 2 (2-0)

92

91

Example 54

Allyl-methyl-dihydrogenated tallow ammonium bentonite (108.8)

0/10

0/10

102

100

Example 55

Ethanol-benzyl-dihydrogenated tallow ammonium bentonite (110)

10/15

2 (2-0) / 15

97

96

Example 56

Ethanol-methyl-dihydrogenated tallow ammonium bentonite (108.2)

10/20

l (3-0) / 20

99

89

Another preferred embodiment of the present invention. It has been found that, in the general case, lubrication

The invention relates to the non-aqueous fluid system containing agents of the type described above not always ideal in their

Lubricant formulations. Behaviors are regarding long exposure and

Up to now, greases mostly contained hydro- _ elevated temperature. Such effects cause a substance oils that were thickened with a soap. In recent years 43 loss of consistency, which has been demonstrated in laboratory tests by a number of non-soap thickeners - an increase in depth of penetration. This does not necessarily mean that the essential advantages over the soaps are always of such a nature that the lubricant is ineffective.

that were used earlier. Likewise, the area has become sam or unusable, but it is clearly desirable to expand a usable lubricant carrier material so that lubricants can be obtained which have their physical characteristics.

also liquids could be used which do not contain hydrocarbons unchanged during the entire use.

are fabric oils, e.g. various esters, silicone oils and holds.

the like. Lubricants of the newer type, as mentioned above, It has now unexpectedly turned out that they are generally used as non-soap-thickened use of the organophilic clays mentioned

Called lubricant. An important sub-group of lubricants allowed, which have an improved stability of these lubricants, are those which are thickened with clay minerals 55 under prolonged working conditions at elevated temperatures, such as, for. B. with montmorillonite and hectorite, and that these lubricants thus produced none which were made organophilic by having a long-chain adverse effects compared to other lubricant properties.

connection. Lubricants of this type have stems, such as. B. Corrosion, behavior towards are described in US Patent No. 2531440 and in various water contaminants and the like,

A publication in the technical literature is described. The lubricating oil-forming base of the lubricant can be anything, such as. B. in the article «Bentone Greases» by C.M. Finlayson is a commonly used oil used in the manufacture of et al., "The Institute Spokesman," May 1950, on the lubricant side, where the thickener described

13-23 and in chapter 17 of the book "Lubricating Greases" by bene organophile Ton. Examples of liquid lubricants

CJ. Boner, New York, 1954. Such lubricants are the same as lubricating oils made from petroleum, sometimes as mineral oil

As usual other lubricants, other additives may contain 65 lubricants, lubricating oils obtained from petroleum, such as. B. corrosion-inhibiting additives, additives for through various polymerization and reforming processes,

extreme pressure tolerance, finely divided solid lubricant. B. the Fischer-Tropsch process, the synthol, synthin

medium, fluorescent additives and the like. and similar processes; Lubricant oils that after

15 652 048

Bergius processes were produced that are of course the same weight ratios in hydrogenation

Coal, peat and the like is used, as well as products related to the organophilic clay used for the

Asphalt, petroleum residues and the like; synthetic lubricants as a whole have been held.

Lubricants, such as those produced by volatilization processes, for example from fatty oils, petroleum hydrocarbon and similar chemicals, so-called ester lubricants. mittein manufactured and evaluated for suitability as lubricant dioctyl phthalate, ethyl ricinoleate and the like, or which alkyl thickener at a concentration of 6%, and or can be alkyl aryl esters, such as. B. tricresyl phosphate; although in common refined oil in the presence of 0.4% synthetic lubricant, which is obtained by polymerization of alky- 10 water. The lubricants were made by making the lenoxides and glycols such as e.g. B. penta gelling agent, the oil and water for 30 minutes with each other methylene glycol and the silicone polymers, which are generally known as mixed while using a drill press, silicone oils are known. which was equipped with inclined mixer blades and at

The organophilic clay reaction product can be operated at any speed of 450 rpm. The desired step in the preparation of the lubricant composition obtained was added with a "trio-homo" dispersant composition. Since the organophilic Tonreak- with a clear width between the rotor and stator of approx.

tion products not treated the presence of a polar activator 0.025 mm. The penetration depths of the fats, according to the requirements, are predispersion with the usual activators ASTM after calming overnight, were obtained after not necessary. Generally, the amounts of Verdik- the lubricants 60 and 10,000 strokes in an engine coolant range from 0.5-10% based on the weight of the lubricated lubricant working condition tester, and these amounts have been found to be effectively exposed. Subject to ASTM. The data so obtained

In addition to the additives mentioned above, those listed in Table VIII. It was also too

Production of the lubricant formulation are used, comparative gelling agents examined so far for comparison purposes,

it has been found that the addition of asbestos in the usually heated lubricant compositions,

Improved thickening effect of organophilic clay. 25 where 2% acetone is used as a polar, organic dispersion medium

The asbestos, which was preferably used in these lubricants for the gelling agent. The lubricants have been brought in, any chrysotile or tremolite can be combined by mixing the gelling agent, oils and acetones.

which is essentially free of non-asbestos-like substances for 30 minutes while heating to 121 ° C under continuous

Slag, and which mechanically or chemically treated animal mixing to expel acetone and then-

so that the phases are separated to such an extent that they are cooled to 82 ° C. and the addition of 0.1% water, so that the respective phases can be mixed without further aids, as described above,

are not visible to the naked eye. There are many ways to do this. The data obtained for these lubricants

which are suitable for carrying out this treatment and which do not contain any organophilic clay will not need to be explained in detail here. It is the data for the lubricants that contain the organophilic clay

Book Asbestos Fundamentals, by Berger and Oesper, New 35 ten, compared in the table because these lubricants are the same

York, 1963, cited. Have composition.

If asbestos is preferred here, it is cheap. The commonly refined oil has the following properties:

to make a dry mix by mixing the organophyne, usually refined clay, with the asbestos. Considering the density ° API at 15 6 ° C 20

relative thickening and stabilizing effects of the organophilic viscosity, SUS at 37.8 ° C 500 in 0.1 Pas len and the asbestos, the practical range of viscosity SUS at 98 9 ° C 53 in 0.1 Pas

Weight of asbestos to organophilic clay in such a viscosity index 12

dry mixture about half to twice the amount of refractive index 1.5085

of the organophilic tone mentioned. Flash point, ° C 199

It is also possible to incorporate a corrosion inhibitor into the 45 yield point, ° C -20.6 lubricant along with the organophilic clay, e.g. Sodium nitrite or similar additives. General- The data show that the organophilic clays of the invention

my said, in the case of the use of nitrite, the fluid system according to the very effective thickener for these oils is a practical range of the concentration of this substance is about that at usual room temperatures, whereby only

0.25 times to 1.0 times the weight of the organophilic clay, 50 little water uses as a dispersant. The data show the applied. It should be noted again that in the same way that the organophilic clays are in the absence of a

In cases where a dry mixture without a lubricating polar organic dispersant is first easily dispersed,

medium oil is produced, it is quite practical, any of which gives lubricants whose penetration depth is equivalent

Sodium nitrite, if present as one of the components, is lent to those lubricants that are used to incorporate into this dry mixture. In such a case 55 of the dispersant can be obtained.

Table VIII

example

Thickener (ME ratio)

consistency

0

60

10,000

Comparative experiment DD

Methyl benzyl dihydrogenated tallow ammonium bentonite (113.6)

297

346

384

Comparative experiment EE

Dimethyl-dihydrogenated tallow ammonium bentonite (95.4) plus activator

238

253

273

Example 57

Allyl ethanol dihydrogenated tallow ammonium bentonite (110.1)

285

338

428

Example 58

Allyl ethanol dihydrogenated tallow ammonium bentonite (118.9)

290

350

442

Example 59

Allyl-methyl-dihydrogenated tallow ammonium bentonite (109.0)

272

322

390

Example 60

Allyl-methyl-dihydrogenated tallow ammonium bentonite (118.0)

295

348

420

Example 61

Allyl-methyl-dihydrogenated tallow ammonium bentonite (119.5)

292

346

415

652 048

16

In another embodiment of the present invention, a vinyl based sealing composition is made. In general, a "sealant" is a material used to exclude air and water from contact with a substrate to which the material is applied. Typically, sealants are used to bond surfaces or fill gaps between layers of glass and metal, and to bond glass to glass, metal to metal, metal to glass, and also to a variety of other substrates. They are also widely used in the manufacture of automobiles, for joining metal parts, filling voids and drip holes, and the like.

A variety of sealant formulations are based on vinyl chloride polymers or resins, and are typically referred to as plastisols, plastic gels, organosols, or organogels depending on the particular sealant formulation. Although these formulations were generally effective as a sealant, the conventional vinyl chloride resin sealant exhibits various undesirable properties when used using conventional theological modifiers, e.g. B. finely ground asbestos, silicon oxide, air gels and organophilic bentonites. For example, there were several disadvantages, the difficulty of adjusting the viscosity, toxic waste recycling problems, especially when using asbestos, and insufficient resistance to drainage as well as product deterioration during melt treatments or welding and plasticizer migration, especially when conventional organophilic bentonites were used.

It has unexpectedly turned out that the systems according to the invention which are described here are suitable for serving as a sealing composition which has preselectable and therefore desirable theological properties, and accordingly it is possible to use such sealing agents essentially for any purpose, for which vinyl chloride sealants have been used so far without having toxic waste disposal problems, and there is no product degradation as was characteristic of prior art materials.

Novel sealing compositions contain a vinyl chloride resin, a plasticizer for the resin and, as an improvement, about 0.1-1.0% of the organophilic clay as described above, which consists of an organic cationic compound and a smectite-type clay which has a cation exchange capacity of at least 75 milliequivalents per 100 g of said clay, and wherein said organic cationic compound has moieties as defined above.

Terms "vinyl chloride polymers or resins" and "polyvinyl chlorides" as used herein generally refer to emulsion quality polyvinyl chloride resins having a molecular weight greater than about 10,000 and an average particle size less than about 10 microns. However, these terms include not only polyvinyl chloride homopolymers of all types, but also copolymers of vinyl chloride as the major fraction, such as copolymers of vinyl chloride that is copolymerized with less than 50% of an ethylenically unsaturated comonomer which is copolymerizable with this. Ethylenically unsaturated comonomers which are copolymerizable with vinyl chloride include vinyl acetate, vinylidene chloride, maleic or fumaric acid, esters, styrene and acetonitrile. Smaller proportions of other synthetic resins, such as. B. chlorinated polyethylene and copolymers of acrylonitrile, butadiene and styrene can also be introduced.

Any conventional plasticizer for vinyl pastes can be used. Particularly desirable materials are the phthalate plasticizers. Typical examples of plasticizers are dialkyl phthalates, such as. Dioctyl phthalate (i.e. di-2-5 ethylhexyl phthalate) and octyldecyl phthalate alkyl phthalyl alkyl glycolates such as e.g. B. ethyl phthalyl ethyl glycolate and butyl phthalyl glycolate; Dialkyl esters of alkanedicarboxylic acids, such as. B. diisobutyl adipate, dî-2-ethylhexaladipate and dibutylse-bazate, acetyltrialkyl citrates, such as. B. acetyltributyl citrate and 10 trialkyl and triaryl phosphates such as e.g. B. trioctyl phosphate, 2-ethylhexyl diphenyl phosphate and tricresyl phosphate. Other useful plasticizers are alkyl esters of fatty acids, e.g. Octyl stearate; epoxidized triglycerides, e.g. B. epoxidized soybean oil and polymeric polyester plasticizers such as e.g. 15 polymeric glycol adipate. White paraffin oil can also be used as a plasticizer. The preferred plasticizers are di-2-ethylhexyl phthalate and diisodecyl phthalate. The plasticizers can be used in amounts of from about 50 to about 300 parts per 100 parts of resin, and preferably from about 70 to about 200 20 parts per 100 parts of resin.

Other conventional additives can also be used, such as. B. fillers, stabilizers and antioxidants. A filler composition primarily serves as a sequestering agent, from which any amount of water contained in the formulation is sequestered. Typical materials include barium sulfate along with either tallow or mica (a type of mica). Other fillers that can be incorporated into the sealing composition include diatomaceous earth, magnesium silicate, calcium silicate, calcium sulfate, titanium dioxide and zinc carbonate. Calcium carbonate coated with calcium stearate can also be used as a filler. The fillers can be used in amounts of about 0-200 parts per 100 parts of resin. 35 Useful stabilizers which are used according to the prior art are, for example, zinc, calcium and aluminum stearates. Other stabilizers are, for example, zinc octoate and tin octoate. A commercial calcium zinc stearate is preferably used together with epoxidized soybean oil. Stabilizers can be present in the compositions in moderate dosages, preferably between 0 and 100 parts, and particularly preferably between 2 and 50 parts per 100 parts of resin.

The sealant composition can be made by any of the usual procedures, such as e.g. B. using mixing machines that are normally used for the production of viscous materials. Because the described rheological additive of the sealing composition can be incorporated without the need for a device for applying high shear forces, conventional mixing is quite suitable without using high-speed shear force mixers, e.g. a Cowles mixer or a waring blendor, as required for organophilic clay compounds that were previously used. In the previous case, mixing can be carried out with a planetary stirrer, with a conventional dough kneader, with a paddle mixer, an extruder or a Banbury mixer or roller mill.

The order of addition of the ingredients is not critical. 60 For example, the rheological additive can be dispersed in the plasticizer before mixing with the resin or it can be added simultaneously with or regardless of the addition of the other components. The sealing formulations can be in the form of a plastisol, 65 a plast gel, an organosole, or an organogel. Accordingly, common volatile liquids can be used to make the sealant.

40

17th

652 048

The following test procedures were used:

Setting test

Using a stainless steel spatula, a seating channel measuring 152.4 mm x approximately 19 mm x approximately 1.27 mm was filled with a sealant (plastisol) formulation (typically 55 g sealant). Once filled, the channel was placed vertically on a 5.08 cm wide surface for one hour at 25 ° C. The settling is determined as the distance in mm that the plastisol moves towards the underlying surface.

Discoloration

The plastisol formulation is placed in an aluminum container with the dimensions of approximately 57.2 mm in diameter and approximately 19 mm in depth. A spatula is then used to smooth the surface of the plastisol and the bowl is placed in a forced air oven at a temperature of 177 ° C

introduced during 15 min. As soon as it cooled to room temperature, the color of the plastisol was assessed.

The plastisol sealant is made by mixing the ingredients listed below in the order in which they are listed. This procedure is common for use in the method according to the invention.

Polyvinylchloride plastisol sealant io diisodecyl phthalate 100 parts

PVC resin, Firestone FPC-6338 100 parts

Mix until the resin is completely dispersed using a dough kneader or a similar mixer and then add it with a mixture of:

CaC03, Camel-wite 160 parts

Stabilizer Tribase 4 parts

Plasticizer, Kodaflex PA-5 26 parts

Rheological additive 10 parts

Table IX

Examples

Rheological additive (ME ratio)

Fineness of the grinding

Viscosity 24 h (IO "3 Pas)

Seed test

Discoloration

Comparative

try FF

Sublimated silicon dioxide

1.0

52Ò0

21st

no

Comparative

try GG

Benzyl dimethyl hydrogenated tallow ammonium bentonite (106.7) ■

0

560

50

moderate to strong

Comparative

try HH

Methyl benzyl dihydrogenated tallow ammonium bentonite (112)

2.0

640

2nd

strong

Example 62

Diallyl-hydrogenated tallow ammonium bentonite (108.4)

1.0

720

0

moderate

Example 63

Allyl-benzyl-dihydrogenated tallow ammonium bentonite (110)

0

760

0

weak

Example 64

Allyl-methyl-dihydrogenated tallow ammonium bentonite (109.8)

3.5

1050

0

strong

Example 65

Ethanol-benzyl-dihydrogenated tallow ammonium bentonite (110)

0

600

0

weak

Example 66

Ethanol-methyl-dihydrogenated tallow ammonium bentonite (108.2)

-

-

0

very weak

Example 67

Triallyl hydrogenated tallow ammonium bentonite (110.2)

1.0

1040

0

strong

M

Claims (14)

652 048 PATENT CLAIMS 1. Non-aqueous fluid system, characterized in that that it contains a non-aqueous composition and an organophilic clay as a rheologically active additive, the additive being a reaction product of an organic cationic compound with a smectite-type clay, which has a cation exchange capacity of at least 75 milliequivalents per 100 g of the above Tones and wherein said organic cationic compound contains the following groups: a) a first group which represents an optionally substituted β, y-unsaturated alkyl or cycloalkyl group with up to 6 carbon atoms or a hydroxy-substituted alkyl or cycloalkyl group with up to 6 carbon atoms which may be substituted with an aromatic radical, b) a second group which is an optionally substituted saturated or unsaturated alkyl group having 12 to 60 carbon atoms, c) a third and fourth group, which comprises the following groups: the groups mentioned under a), optionally substituted aralkyl groups, optionally substituted alkyl or cycloalkyl groups having up to 22 carbon atoms and mixtures thereof, and the amount of the organic cationic compound is 90 to 140 milliequivalents per 100 g of the clay, based on 100% active clay. 2. Fluid system according to claim 1, characterized in that the clay of the smectite type is hectorite and / or sodium bentonite. 3. Fluid system according to claim 1 or 2, characterized in that the ß, y-unsaturated optionally substituted alkyl or cycloalkyl group has up to 6 carbon atoms, the alkyl group preferably having aromatic groups or having aromatic groups which are further substituted by aliphatic groups are substituted. 4. Fluid system according to one of claims 1 to 3, characterized in that the hydroxy-substituted alkyl or cycloalkyl group has 2 to 6 carbon atoms, the hydroxy substituent being on the carbon atoms 2-6. 5. Fluid system according to one of claims 1 to 4, characterized in that the organic cationic compound is a phosphonium compound or a quaternary ammonium compound. 6. Fluid system according to one of claims 1 to 5, characterized in that the aliphatic group of grouping (b) is an alkyl group or an alkenyl group having 12 to 22 carbon atoms. 7. Fluid system according to claim 6, characterized in that the alkyl group or alkenyl group is derived from a long-chain fatty acid group. 8. Fluid system according to one of claims 1 to 7, characterized in that the amount of said organic cationic compound in the range of 100-130 milliequivalents per 100 g of said clay, calculated on the basis of 100% active clay. 9. Fluid system according to one of the claims 1 to 8, characterized in that the organophilic clay makes up 0.1 to 15% by weight, preferably 0.3 to 5.0% by weight of the non-aqueous fluid system mentioned. 10. Fluid system according to claim 1, characterized in that said organic cationic compound is one of the formula 10th R < R> X R, M wherein in this formula Ri comprises a β-y-unsaturated alkyl group or hydroxyalkyl group with up to 6 carbon atoms; R2 represents an alkyl group having 12 to 60 carbon atoms 15; R3 and R4 correspond to the groups specified in claim 1 under (a) and include aralkyl groups, alkyl groups having 1 to 22 carbon atoms and mixtures thereof; X represents a phosphorus or nitrogen atom and M \ Cl ", Br", NO "2, OH 'or C2H3O2". 11. A non-aqueous fluid system according to claim 1, characterized in that it is a paint composition, an organic printing ink, a lubricating oil or a sealing formulation based on polyvinyl chloride homopolymers and / or copolymers, the non-aqueous composition being the film-forming material. 12. Non-aqueous fluid system according to claim 11, characterized in that it is a paint composition and additionally contains a finely divided pigment in an amount of 0.25-10% by weight, based on the system, in dispersed form. 13. A non-aqueous fluid system according to claim 11, characterized in that it is an organic printing ink and additionally contains an ink coloring material dispersed. 14. Non-aqueous fluid system according to claim 11, characterized in that the smectite-type clay is hectorite and / or sodium bentonite. 20th 25th 30th 35 45